Laundry detergent compositions with polyamide-polyamines

ABSTRACT

Detergent compositions and fabric laundering and treating methods utilize certain polyamide-polyamines as fabric treatment agents that can impart fabric appearance benefits to fabric laundered or treated in washing or soaking solutions which contain such agents. Such polyamide-polyamine fabric treatment agents include adipic acid-diethylenetriamine-epichlorohydrin adducts.

The present application claims priority to Provisional Application60/033,964, filed Dec. 31, 1996.

TECHNICAL FIELD

The present invention relates to heavy duty laundry detergentcompositions, in either liquid or granular form, which contain certaintypes of polyamide-polyamine materials to impart appearance benefits tofabrics and textiles laundered in washing solutions formed from suchcompositions.

BACKGROUND OF THE INVENTION

It is, of course, well known that alternating cycles of using andlaundering fabrics and textiles, such as articles of worn clothing andapparel, will inevitably adversely affect the appearance and integrityof the fabric and textile items so used and laundered. Fabrics andtextiles simply wear out over time and with use. Laundering of fabricsand textiles is necessary to remove soils and stains which accumulatetherein and thereon during ordinary use. However, the launderingoperation itself, over many cycles, can accentuate and contribute to thedeterioration of the appearance of such fabrics and textiles.

Deterioration of fabric appearance can manifest itself in several ways.Short fibers are dislodged from woven and knit fabric/textile structuresby the mechanical action of laundering. These dislodged fibers may formlint, fuzz or "prills" which are visible on the surface of fabrics anddiminish the appearance of newness of the fabric. Further, repeatedlaundering of fabrics and textiles, especially with bleach-containinglaundry products, can remove dye from fabrics and textiles and impart afaded, worn out appearance as a result of diminished color intensity,and in many cases, as a result of changes in hues or shades of color.

Given the foregoing, there is clearly an ongoing need to identifymaterials which could be added to laundry detergent products that wouldassociate themselves with the fibers of the fabrics and textileslaundered using such detergent products and thereby reduce or minimizethe tendency of the laundered fabric/textiles to deteriorate inappearance. Any such detergent product additive material should, ofcourse, be able to benefit fabric appearance without unduly interferingwith the ability of the laundry detergent to perform its fabric cleaningfunction. The present invention is directed to detergent compositionscontaining certain types of polyamide-polyamine materials that performin this desired manner.

SUMMARY OF THE INVENTION

The laundry detergent compositions herein comprise from about 1% to 80%by weight of a detersive surfactant, from about 0.1% to 80% by weight ofan organic or inorganic detergency builder and from about 0.1% to 8% byweight of certain types of polyamide-polyamine fabric treatment agents.The detersive surfactant and detergency builder materials can be any ofthose useful in conventional laundry detergent products. Thepolyamide-polyamine materials are those which are comprised of repeatingamido-amine units which may be substituted and/or derivatized as shownin the general Structural Formula No. I set forth hereinafter in the"Detailed Description of the Invention" section.

Particularly preferred polyamide-polyamine materials for use in thedetergent and fabric treatment compositons herein comprise the reactionproducts of epichlorohydrin with polyamide-polyamines formed from adipicacid and diethylenetriamine. Such materials are commercially availableunder the tradename Kymene®.

In its method aspect, the present invention relates to the laundering ortreating of fabrics and textiles in aqueous washing or treatingsolutions formed from effective amounts of the detergent compositionsdescribed herein, or formed from the individual components of suchcompositions. Laundering of fabrics and textiles in such washingsolutions, followed by rinsing and drying, imparts fabric appearancebenefits to the fabric and textile articles so treated. Such benefitscan include improved overall appearance, prills/fuzz reduction, andantifading.

DETAILED DESCRIPTION OF THE INVENTION

As noted, the laundry detergent compositions of the present inventionessentially contain detersive surfactant, detergent builder and certainpolyamide-polyamine fabric treatment agents which serve to enhancefabric appearance upon use of the detergent compositions to launderfabrics and textiles. Each of these essential detergent compositioncomponents, as well as optional ingredients for such compositions andmethods of using such compositions, are described in detail as follows:All percentages and ratios given are by weight unless other specified.

A) Detersive Surfactant

The detergent compositions herein essentially comprise from about 1% to80% by weight of a detersive surfactant. Preferably such compositionscomprise from about 5% to 50% by weight of this surfactant. Detersivesurfactants utilized can be of the anionic, nonionic, zwitterionic,ampholytic or cationic type or can comprise compatible mixtures of thesetypes. Detergent surfactants useful herein are described in U.S. Pat.No. 3,664,961, Norris, Issued May 23, 1972; U.S. Pat. No. 3,919,678,Laughlin et al., Issued Dec. 30, 1975; U.S. Pat. No. 4,222,905,Cockrell, Issued Sep. 16, 1980; and in U.S. Pat. No. 4,239,659, Murphy,Issued Dec. 16, 1980. All of these patents are incorporated herein byreference. Of all the surfactants, anionics and nonionics are preferred.

Useful anionic surfactants can themselves be of several different types.For example, water-soluble salts of the higher fatty acids, i.e.,"soaps", are useful anionic surfactants in the compositions herein. Thisincludes alkali metal soaps such as the sodiun, potassium, ammonium, andalkylolammonium salts of higher fatty acids containing from about 8 toabout 24 carbon atoms, and preferably from about 12 to about 18 carbonatoms. Soaps can be made by direct saponification of fats and oils or bythe neutralization of free fatty acids. Particularly useful are thesodium and potassium salts of the mixtures of fatty acids derived fromcoconut oil and tallow, i.e., sodium or potassium tallow and coconutsoap.

Additional non-soap anionic surfactants which are suitable for useherein include the water-soluble salts, preferably the alkali metal, andammonium salts, of organic sulfuric reaction products having in theirmolecular structure an alkyl group containing from about 10 to about 20carbon atoms and a sulfonic acid or sulfuric acid ester group. (Includedin the term "alkyl" is the alkyl portion of acyl groups.) Examples ofthis group of synthetic surfactants are a) the sodium, potassium andammonium alkyl sulfates, especially those obtained by sulfating thehigher alcohols (C₈ -C₁₈ carbon atoms) such as those produced byreducing the glycerides of tallow or coconut oil; b) the sodium,potassium and ammonium alkyl polyethoxylate sulfates, particularly thosein which the alkyl group contains from 10 to 22, preferably from 12 to18 carbon atoms, and wherein the polyethoxylate chain contains from 1 to15, preferably 1 to 6 ethoxylate moieties; and c) the sodium andpotassium alkylbenzene sulfonates in which the alkyl group contains fromabout 9 to about 15 carbon atoms, in straight chain or branched chainconfiguration, e.g., those of the type described in U.S. Pat. Nos.2,220,099 and 2,477,383. Especially valuable are linear straight chainalkylbenzene sulfonates in which the average number of carbon atoms inthe alkyl group is from about 11 to 13, abbreviated as C₁₁₋₁₃ LAS.

Preferred nonionic surfactants are those of the formula R¹ (OC² H₄)_(n)OH, wherein R¹ is a C₁₀ -C₁₆ alkyl group or a C₈ -C₁₂ alkyl phenylgroup, and n is from 3 to about 80. Particularly preferred arecondensation products of C₁₂ -C₁₅ alcohols with from about 5 to about 20moles of ethylene oxide per mole of alcohol, e.g., C₁₂ -C₁₃ alcoholcondensed with about 6.5 moles of ethylene oxide per mole of alcohol.

Additional suitable nonionic surfactants include polyhydroxy fatty acidamides of the formula: ##STR1## wherein R is a C₉₋₁₇ alkyl or alkenyl,R₁ is a methyl group and Z is glycityl derived from a reduced sugar oralkoxylated derivative thereof. Examples are N-methyl N-1-deoxyglucitylcocoamide and N-methyl N-1-deoxyglucityl oleamide. Processes for makingpolyhydroxy fatty acid amides are known and can be found in Wilson, U.S.Pat. No. 2,965,576 and Schwartz, U.S. Pat. No. 2,703,798, thedisclosures of which are incorporated herein by reference.

B) Detergent Builder

The detergent compositions herein also essentially comprise from about0.1% to 80% by weight of a detergent builder. Preferably suchcompositions in liquid form will comprise from about 1% to 10% by weightof the builder component. Preferably such compositions in granular formwill comprise from about 1% to 50% by weight of the builder component.Detergent builders are well known in the art and can comprise, forexample, phosphate salts as well as various organic and inorganicnonphosphorus builders.

Water-soluble, nonphosphorus organic builders useful herein include thevarious alkali metal, ammonium and substituted ammonium polyacetates,carboxylates, polycarboxylates and polyhydroxy sulfonates. Examples ofpolyacetate and polycarboxylate builders are the sodium, potassium,lithium, ammonium and substituted ammonium salts of ethylene diaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melliticacid, benzene polycarboxylic acids, and citric acid. Other suitablepolycarboxylates for use herein are the polyacetal carboxylatesdescribed in U.S. Pat. No. 4,144,226, issued Mar. 13, 1979 toCrutchfield et al, and U.S. Pat. No. 4,246,495, issued Mar. 27, 1979 toCrutchfield et al, both of which are incorporated herein by reference.Particularly preferred polycarboxylate builders are the oxydisuccinatesand the ether carboxylate builder compositions comprising a combinationof tartrate monosuccinate and tartrate disuccinate described in U.S.Pat. No. 4,663,071, Bush et al., issued May 5, 1987, the disclosure ofwhich is incorporated herein by reference.

Examples of suitable nonphosphorus, inorganic builders include thesilicates, aluminosilicates, borates and carbonates. Particularlypreferred are sodium and potassium carbonate, bicarbonate,sesquicarbonate, tetraborate decahydrate, and silicates having a weightratio of SiO₂ to alkali metal oxide of from about 0.5 to about 4.0,preferably from about 1.0 to about 2.4. Also preferred arealuminosilicates including zeolites. Such materials and their use asdetergent builders are more fully discussed in Corkill et al, U.S. Pat.No. 4,605,509, the disclosure of which is incorporated herein byreference. Also, crystalline layered silicates such as those discussedin Corkill et al, U.S. Pat. No. 4,605,509, incorporated herein byreference, are suitable for use in the detergent compositions of thisinvention.

C) Polyamide-Polyamine Materials

The third essential component of the detergent compositions hereincomprises one or more polyamide-polyamine materials fabric treatmentagents. Such materials have been found to impart a number of appearancebenefits to fabrics and textiles laundered in aqueous washing solutionsformed from detergent compositions which contain suchpolyamide-polyamines. These fabric appearance benefits can include, forexample, improved overall appearance of the laundered fabrics, reductionof the formation of prills and fizz, protection against color fading,etc. The polyamine-polyamide polymers used in the compositions andmethods herein can provide such fabric appearance benefits withacceptably little or no loss in cleaning performance provided by thelaundry detergent compositions into which such materials areincorporated.

The polyamide-polyamines useful herein will generally comprise fromabout 0.1% to 8% by the weight of the composition. More preferably, suchpolyamide-polyamine materials will comprise from about 0.5% to 4% byweight of the compositions herein. Most preferably, thesepolyamide-polyamines will comprise from about 1% to 3% by weight of thecomposition.

The polyamide-polyamine materials used in this invention are those whichhave repeating, substituted amido-amine units which correspond to thegeneral Structural Formula No. I as follows: ##STR2##

In Structural Formula No. I, R₁, R₂ and R₅ are each independently C₁₋₄alkylene, C₁₋₄ alkarylene or arylene. It is also possible to eliminateR₁ entirely so that the polyamide-polyamine is derived from oxalic acid.

Also in Structural Formula No. I, R₃ is H, epichlorohydrin, anazetidinium group, an epoxypropyl group or a dimethylaminohydroxypropylgroup, and R₄ can be H, C₁₋₄ alkyl, C₁₋₄ alkaryl, or aryl. R₄ may alsobe any of the foregoing groups condensed with C₁₋₄ alkylene oxide.

R₁ is preferably butylene, and R₂ and R₅ are preferably ethylene. R₃ ispreferably epichlorohydrin. R₄ is preferably H.

The polyamide-polyamine materials useful herein can be prepared byreacting polyamines such as diethylenetriamine, triethylenetetraamine,tetraethylenepentamine or dipropylenetriamine with C₂ -C₁₂ dicarboxylicacids such as oxalic, succinic, glutaric, adipic and diglycolic acids.Such materials may then be further derivatized by reaction with, forexample, epichiorohydrin. Preparation of such materials is described ingreater detail in Keim, U.S. Pat. No. 2,296,116, Issued Feb. 23, 1960;Keim, U.S. Pat. No. 2,296,154, Issued Feb. 23, 1960 and Keim, U.S. Pat.No. 3,332,901, Issued Jul. 25, 1967. The disclosures of all three ofthese patents are incorporated herein by reference.

The polyamide-polyamine-epichlorohydrin fabric treatment agentspreferred for use herein are commercially marketed by Hercules, Inc.under the tradename Kymene® Especially useful are Kymene 557H® andKymene 557LX® which are epichlorohydrin adducts of polyamide-polyamineswhich are the reaction products of diethylenetriamine and adipic acid.Other suitable materials are those marketed by Hercules under thetradenames Reten® and Delsette®, and by Sandoz under the tradenameCartaretin®. These polyamide-polyamine materials are marketed in theform of aqueous suspensions of the polymeric material containing, forexample, about 12.5% by weight of solids.

D) Optional Detergent Ingredients

In addition to the essential surfactants, builders andpolyamide-polyamines hereinbefore described, the detergent compositionof the present invention can also include any number of additionaloptional ingredients. These include conventional detergent compositioncomponents such as bleaches and bleach activators, enzymes and enzymestabilizing agents, suds boosters or suds suppressers, anti-tarnish andanticorrosion agents, soil suspending agents, soil release agents,germicides, pH adjusting agents, non-builder alkalinity sources,chelating agents, organic and inorganic fillers, solvents, hydrotropes,optical brighteners, dyes and perfumes.

A preferred optional ingredients for incorporation into the detergentcompositions herein comprises a bleaching agent, e.g., a peroxygenbleach. Such peroxygen bleaching agents may be organic or inorganic innature. Inorganic peroxygen bleaching agents are frequently utilized incombination with a bleach activator.

Useful organic peroxygen bleaching agents include percarboxylic acidbleaching agents and salts thereof. Suitable examples of this class ofagents include magnesium monoperoxyphthalate hexahydrate, the magnesiumsalt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acidand diperoxydodecanedioic acid. Such bleaching agents are disclosed inU.S. Pat. No. 4,483,781, Hartman, Issued Nov. 20, 1984; European PatentApplication EP-A-133,354, Banks et al., Published Feb. 20, 1985; andU.S. Pat. No. 4,412,934, Chung et al., Issued Nov. 1, 1983. Highlypreferred bleaching agents also include ⁶ -nonylamino-6-oxoperoxycaproicacid (NAPAA) as described in U.S. Pat. No. 4,634,551, Issued Jan. 6,1987 to Burns et al.

Inorganic peroxygen bleaching agents may also be used, generally inparticulate form, in the detergent compositions herein. Inorganicbleaching agents are in fact preferred. Such inorganic peroxygencompounds include alkali metal perborate and percarbonate materials. Forexample, sodium perborate (e.g. mono- or tetra-hydrate) can be used.Suitable inorganic bleaching agents can also include sodium or potassiumcarbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodiumpyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) canalso be used. Frequently inorganic peroxygen bleaches will be coatedwith silicate, borate, sulfate or water-soluble surfactants. Forexample, coated percarbonate particles are available from variouscommercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa.

Inorganic peroxygen bleaching agents, e.g., the perborates, thepercarbonates, etc., are preferably combined with bleach activators,which lead to the in situ production in aqueous solution (i.e., duringuse of the compositions herein for fabric laundering/bleaching) of theperoxy acid corresponding to the bleach activator. Various non-limitingexamples of activators are disclosed in U.S. Pat. No. 4,915,854, IssuedApr. 10, 1990 to Mao et al.; and U.S. Pat. No. 4,412,934 Issued Nov. 1,1983 to Chung et al. The nonanoyloxybenzene sulfonate (NOBS) andtetraacetyl ethylene diamine (TAED) activators are typical andpreferred. Mixtures thereof can also be used. See also the hereinbeforereferenced U.S. Pat. No. 4,634,551 for other typical bleaches andactivators useful herein.

Other useful amido-derived bleach activators are those of the formulae:

    R.sup.1 N(R.sup.5)C(O)R.sup.2 C(O)L or R.sup.1 C(O)N(R.sup.5)R.sup.2 C(O)L

wherein R¹ is an alkyl group containing from about 6 to about 12 carbonatoms, R² is an alkylene containing from 1 to about 6 carbon atoms, R⁵is H or alkyl, aryl, or alkaryl containing from about 1 to about 10carbon atoms, and L is any suitable leaving group. A leaving group isany group that is displaced from the bleach activator as a consequenceof the nucleophilic attack on the bleach activator by the perhydrolysisanion. A preferred leaving group is phenol sulfonate.

Preferred examples of bleach activators of the above formulae include(6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate andmixtures thereof as described in the hereinbefore referenced U.S. Pat.No. 4,634,551.

Another class of useful bleach activators comprises the benzoxazin-typeactivators disclosed by Hodge et al. in U.S. Pat. No. 4,966,723, IssuedOct. 30, 1990, incorporated herein by reference. A highly preferredactivator of the benzoxazin-type is: ##STR3##

Still another class of useful bleach activators includes the acyl lactamactivators, especially acyl caprolactams and acyl valerolactams of theformulae: ##STR4## wherein R⁶ is H or an alkyl, aryl, alkoxyaryl, oralkaryl group containing from 1 to about 12 carbon atoms. Highlypreferred lactam activators include benzoyl caprolactam, octanoylcaprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam,decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam,octanoyl valerolactam, nonanoyl valerolactam, decanoyl valerolactam,undecenoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam andmixtures thereof. See also U.S. Pat. No. 4,545,784, Issued to Sanderson,Oct. 8, 1985, incorporated herein by reference, which discloses acylcaprolactams, including benzoyl caprolactam, adsorbed into sodiumperborate.

If utilized, peroxygen bleaching agent will generally comprise fromabout 2% to 30% by weight of the detergent compositions herein. Morepreferably, peroxygen bleaching agent will comprise from about 2% to 20%by weight of the compositions. Most preferably, peroxygen bleachingagent will be present to the extent of from about 3% to 15% by weight ofthe compositions herein. If utilized, bleach activators can comprisefrom about 2% to 10% by weight of the detergent compositions herein.Frequently, activators are employed such that the molar ratio ofbleaching agent to activator ranges from about 1:1 to 10:1, morepreferably from about 1.5:1 to 5:1.

Another highly preferred optional ingredient in the detergentcompositions herein is a detersive enzymes component. Enzymes can beincluded in the present detergent compositions for a variety ofpurposes, including removal of protein-based, carbohydrate-based, ortriglyceride-based stains from substrates, for the prevention of refugeedye transfer in fabric laundering, and for fabric restoration. Suitableenzymes include proteases, amylases, lipases, cellulases, peroxidases,and mixtures thereof of any suitable origin, such as vegetable, animal,bacterial, fungal and yeast origin. Preferred selections are influencedby factors such as pH-activity and/or stability optima, thermostability,and stability to active detergents, builders and the like. In thisrespect bacterial or fimgal enzymes are preferred, such as bacterialamylases and proteases, and fungal cellulases.

"Detersive enzyme", as used herein, means any enzyme having a cleaning,stain removing or otherwise beneficial effect in a laundry detergentcomposition. Preferred enzymes for laundry purposes include, but are notlimited to, proteases, cellulases, lipases, amylases and peroxidases.

Enzymes are normally incorporated into detergent compositions at levelssufficient to provide a "cleaning-effective amount". The term"cleaning-effective amount" refers to any amount capable of producing acleaning, stain removal, soil removal, whitening, deodorizing, orfreshness improving effect on substrates such as fabrics. In practicalterms for current commercial preparations, typical amounts are up toabout 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzymeper gram of the detergent composition. Stated otherwise, thecompositions herein will typically comprise from 0.001% to 5%,preferably 0.01%-1% by weight of a commercial enzyme preparation.Protease enzymes are usually present in such commercial preparations atlevels sufficient to provide from 0.005 to 0.1 Anson units (AU) ofactivity per gram of composition. Higher active levels may be desirablein highly concentrated detergent formulations.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniformis. Onesuitable protease is obtained from a strain of Bacillus, having maximumactivity throughout the pH range of 8-12, developed and sold asESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". Thepreparation of this enzyme and analogous enzymes is described in GB1,243,784 to Novo. Other suitable proteases include ALCALASE® andSAVINASE® from Novo and MAXATASE® from International Bio-Synthetics,Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756A, Jan. 9, 1985 and Protease B as disclosed in EP 303,761 A, Apr. 28,1987 and EP 130,756 A, Jan. 9, 1985. See also a high pH protease fromBacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymaticdetergents comprising protease, one or more other enzymes, and areversible protease inhibitor are described in WO 9203529 A to Novo.Other preferred proteases include those of WO 9510591 A to Procter &Gamble. When desired, a protease having decreased adsorption andincreased hydrolysis is available as described in WO 9507791 to Procter& Gamble. A recombinant trypsin-like protease for detergents suitableherein is described in WO 9425583 to Novo.

Cellulases usable herein include both bacterial and fungal types,preferably having a pH optimum between 5 and 10. U.S. Pat. No.4,435,307, Barbesgoard et al, Mar. 6, 1984, discloses suitable fungalcellulases from Humicola insolens or Humicola strain DSM1800 or acellulase 212-producing fungus belonging to the genus Aeromonas, andcellulase extracted from the hepatopancreas of a marine mollusk,Dolabella Auricula Solander. Suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME® andCELLUZYME® (Novo) are especially useful. See also WO 9117243 to Novo.

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19,154, as disclosed in GB 1,372,034. See also lipases in JapaneseApplication 53,20487, laid open Feb. 24, 1978. This lipase is availablefrom Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade nameLipase P "Amano," or "Amano-P." Other suitable commercial lipasesinclude Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacterviscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan;Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. andDisoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.LIPOLASE® enzyme derived from Humicola lanuginosa and commerciallyavailable from Novo, see also EP 341,947, is a preferred lipase for useherein.

The enzyme-containing compositions herein may optionally also comprisefrom about 0.001% to about 10%, preferably from about 0.005% to about8%, most preferably from about 0.01% to about 6%, by weight of an enzymestabilizing system. The enzyme stabilizing system can be any stabilizingsystem which is compatible with the detersive enzyme. Such a system maybe inherently provided by other formulation actives, or be addedseparately, e.g., by the formulator or by a manufacturer ofdetergent-ready enzymes. Such stabilizing systems can, for example,comprise calcium ion, boric acid, propylene glycol, short chaincarboxylic acids, boronic acids, and mixtures thereof, and are designedto address different stabilization problems depending on the type andphysical form of the detergent composition.

E) Detergent Composition Preparation

The detergent compositions according to the present invention can be inliquid, paste or granular forms. Such compositions can be prepared bycombining the essential and optional components in the requisiteconcentrations in any suitable order and by any conventional means.

Granular compositions, for example, are generally made by combining basegranule ingredients (e.g. surfactants, builders, water, etc.) as aslurry, and spray drying the resulting slurry to a low level of residualmoisture (5-12%). The remaining dry ingredients can be admixed ingranular powder form with the spray dried granules in a rotary mixingdrum and the liquid ingredients (e.g. aqueous suspensions of theessential polyamide-polyamines, enzymes, binders and perfumes) can besprayed onto the resulting granules to form the finished detergentcomposition. Granular compositions according to the present inventioncan also be in "compact form", i.e. they may have a relatively higherdensity than conventional granular detergents, i.e. from 550 to 950 g/l.In such case, the granular detergent compositions according to thepresent invention will contain a lower amount of "inorganic fillersalt", compared to conventional granular detergents; typical fillersalts are alkaline earth metal salts of sulphates and chlorides,typically sodium sulphate; "compact" detergents typically comprise notmore than 10% filler salt.

Liquid detergent compositions can be prepared by admixing the essentialand optional ingredients thereof in any desired order to providecompositions containing components in the requisite concentrations.Liquid compositions according to the present invention can also be in"compact form", in such case, the liquid detergent compositionsaccording to the present invention will contain a lower amount of water,compared to conventional liquid detergents.

Addition of the polyamide-polyamine component to liquid detergentcompositions of this invention may be accomplished by simply mixing intothe liquid detergent aqueous suspensions of the desiredpolyamide-polyamine. Such polyamide-polyamide materials can alter theviscosity or other rheological characteristics of liquid detergentproducts. It may therefore be necessary to compensate for anyrheological changes in the liquid detergent product brought about bypolyamide-polyamine addition by altering the type and amount ofhydrotropes and/or solvents that are used.

F) Fabric Laundering Method

The present invention also provides a method for laundering fabrics in amanner which imparts fabric appearance benefits provided by thepolyamide-polyamine materials used herein. Such a method employscontacting these fabrics with an aqueous washing solution formed from aneffective amount of the detergent compositions hereinbefore described orformed from the individual components of such compositions. Contactingof fabrics with washing solution will generally occur under conditionsof agitation although the compositions of the present invention may alsobe used to form aqueous unagitated soaking solutions for fabric cleaningand treatment.

Agitation is preferably provided in a washing machine for good cleaning.Washing is preferably followed by drying the wet fabric in aconventional clothes dryer. An effective amount of the liquid orgranular detergent composition in the aqueous wash solution in thewashing machine is preferably from about 500 to about 7000 ppm, morepreferably from about 1000 to about 3000 ppm.

G) Fabric Conditioning

The polyamide-polyamines hereinbefore described as components of thelaundry detergent compositions herein may also be used to treat andcondition fabrics and textiles in the absence of the surfactant andbuilder components of the detergent composition embodiments of thisinvention. Thus, for example, a fabric conditioning compositioncomprising only the polyamide-polyamines themselves, or comprising anaqueous solution or suspension of the polyamide-polyamines, may be addedduring the rinse cycle of a conventional home laundering operation inorder to impart the desired fabric appearance benefits hereinbeforedescribed.

EXAMPLES

The following examples illustrate the compositions of the presentinvention, but are not necessarily meant to limit or otherwise definethe scope of the invention.

Examples 1-24 Liquid Detergent Test Composition Preparation

Several heavy duty liquid (HDL) detergent compositions are preparedcontaining various polyamide-polyamines. Such liquid detergentcompositions all have the following basic formula:

    ______________________________________                                        Component                  Wt. %                                              ______________________________________                                        C.sub.12-15 alkyl ether (2.5) sulfate                                                                    19.0                                                 C.sub.12-13 alkyl ethoxylate (9.0) 2.00                                       C.sub.12-14 glucose amide 3.50                                                Citric Acid 3.00                                                              C.sub.12-14 Fatty Acid 2.00                                                   MEA to pH 8                                                                   Ethanol 3.41                                                                  Propanediol 6.51                                                              Borax 2.5                                                                     Dispersant 1.18                                                               Na Toluene Sulfonate 2.50                                                     Polyamide-polyamine (See Table 1) as in Table 1                               Dye, Perfume, Brighteners, Enzymes, Preservatives, Suds Balance                                         Suppressor, Other Minors, Water                      100%                                                                       ______________________________________                                    

                  TABLE 1                                                         ______________________________________                                        Polyamides Used in Liquid Test Detergents                                       Example                           Wt. %                                       #  Polyamide Supplier Active in HDL                                         ______________________________________                                        1      Kymene 557H       Hercules 3.2                                           2 Kymene 557H Hercules 2.0                                                    3 Kymene 557H Hercules 1.6                                                    4 Kymene 557 LX Hercules 3.2                                                  5 Kymene 557 LX Hercules 2.0                                                  6 Kymene 450 Hercuies 3.2                                                     7 Kymene 450 Hercules 2.0                                                     8 Reten 201 Hercules 3.2                                                      9 Reten 203 Hercules 3.2                                                      10 Delsette 101 Hercules 6.4                                                  11 Delsette 101 Hercules 4.8                                                  12 Delsette 101 Hercules 3.2                                                  13 Delsette 101 Hercules 1.6                                                  14 Cartaretin F4 Sandoz 4.8                                                   15 Cartaretin F4 Sandoz 1.6                                                   16 Cataretin F23 Sandoz 1.6                                                   17 Polymer 567 (adipic acid/DETA Hercules 4.8                                  copolymer)                                                                   18 Polymer 567 (adipic acid/DETA Hercules 1.6                                  copolymer)                                                                   19 adipic acid/DETA copolymer - Hercules 3.2                                   32% methyl substituted                                                       20 adipic acid/DETA colpolymer - Hercules 3.2                                  63% methyl substituted                                                       21 adipic acid/DETA copolymer - Hercules 3.2                                   84% methyl substituted                                                       22 adipic acid/DETA copolymer - Hercules 3.2                                   25% epichlorohydrin substituted                                              23 adipic acid/DETA copolymer - Hercules 3.2                                   50% epichlorohydrin substituted                                              24 adipic acid/DETA copolymer - Hercules 3.2                                   75% epichlorohydrin substituted                                            ______________________________________                                    

Example 25-48 Granular Detergent Test Composition Preparation

Several heavy duty granular (HDG) detergent compositions are preparedcontaining various polyamide-polyamines. Such granular detergentcompositions all have the following basic formula:

    ______________________________________                                        Component                 Wt. %                                               ______________________________________                                        C.sub.12 Linear alkyl benzene sulfonate                                                                 9.31                                                  C.sub.14-15 alkyl sulfonate 12.74                                             Zeolite Builder 27.79                                                         Sodium Carbonate 27.31                                                        PEG 4000 1.60                                                                 Dispersant 2.26                                                               C.sub.12-13 alkyl ethoxylate (E9) 1.5                                         Sodium Perborate 1.03                                                         Soil Release Polymer 0.41                                                     Enzymes 0.59                                                                  Polyamide-polyamine as in Table 2                                             Perfume, Brightener, Suds Suppressor, Other Minors, Balance                   Moisture, Sulfate                                                              100%                                                                       ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Polyamides Used in Granular Test Detergents                                     Example                           Wt. %                                       #  Polyamide Supplier Active in HDG                                         ______________________________________                                        25     Kymene 557H       Hercules 1.0                                           26 Kymene 557H Hercules 1.5                                                   27 Kymene 557H Hercules 2.0                                                   28 Kymene 557 LX Hercules 2.0                                                 29 Kymene 557 LX Hercules 2.5                                                 30 Kymene 450 Hercules 2.0                                                    31 Kymene 450 Hercules 2.5                                                    32 Reten 201 Hercules 2.0                                                     33 Reten 203 Hercules 2.5                                                     34 Delsette 101 Hercules 1.0                                                  35 Delsette 101 Hercules 1.8                                                  36 Delsette 101 Hercules 2.4                                                  37 Delsette 101 Hercules 3.2                                                  38 Cartaretin F4 Saridoz 2.0                                                  39 Cartaretin F4 Sandoz 2.5                                                   40 Cartaretin F23 Sandoz 2.5                                                  41 Polymer 567 (adipic Hercules 2.0                                            acid/DETA copolymer)                                                         42 Polymer 567 (adipic Hercules 2.5                                            acid/DETA copolymer)                                                         43 adipic acid/DETA copolymer - Hercules 2.5                                   32% methyl substituted                                                       44 adipic acid/DETA copolymer - Hercules 2.5                                   63% methyl substituted                                                       45 adipic acid/DETA copolymer - Hercules 2.5                                   84% methyl substituted                                                       46 adipic acid/DETA copolymer - Hercules 2.5                                   25% epichlorohydrin                                                           substituted                                                                  47 adipic acid/DETA copolymer - Hercules 2.5                                   50% epichlorohydrin                                                           substituted                                                                  48 adipic acid/DETA copolymer - Hercules 2.5                                   75% epichlorohydrin                                                           substituted                                                                ______________________________________                                    

What is claimed is:
 1. A granular laundry detergent composition whichimparts fabric appearance benefits, including pRill/fuzz reduction andantifading, to fabrics and textiles laundered in aqueous washingsolutions formed therefrom, said composition comprising:A) from 5% to50% by weight of a detersive surfactant; B) from 1% to 50% by weight ofan organic or inorganic detergency builder; C) from 0.1% to 8% by weightof a polyamide-polyamine fabric treatment agent formed from repeatingunits of the structural formula: ##STR5## wherein R₁, R₂ and R₅ are eachindependently C₁₋₄ alkylene, C₁₋₄ alkarylene or arylene, or wherein R₁may not be present;wherein R₃ is H, epichiorohydrin, an azetidiniumgroup, an epoxypropyl group or a dimethylaminohydroxypropyl group; andwherein R₄ is H, C₁₋₄ alkyl, C₁₋₄ alkaryl, or aryl groups, and whereinsaid R₄ groups may optionally be condensed with C₁₋₄ alkylene oxide; andD) from 0.001% to 5%, by weight, enzyme.
 2. A laundry detergentcomposition according to claim 1, wherein the enzyme e is selected fromthe group consisting of proteases, cellulases, lipases, amylases,peroxidases and mixtures thereof, and wherein the laundry detergentcomposition further comprises from about 0.00 1% to about 10%, byweight, of an enzyme stabilizing system.
 3. A laundry detergentcomposition according to claim 1, comprising from 1.5% to 8% by weightof the polyamide-polyamine fabric treatment agent.
 4. A laundrydetergent composition according to claim 1, wherein the detergencybuilder is selected from the group consisting of aluminosilicates,silicates and mixtures thereof.
 5. A laundry detergent compositionaccording to claim 1, further comprising a peroxygen bleaching agent anda bleach activator in a weight ratio of peroxygen bleaching agent tobleach activator of from about 1:1 to 10:1.
 6. A laundry detergentcomposition according to claim 1, wherein the bleach activator isselected from the group consisting of nonanyloxybenzene sulfonate;tetraacetyl ethylene diamine; (6-octanamidocaproyl) oxybenzenesulfonate(6-nonanamidocaproyl)oxybenzenesulfonate; (6-decanamidocaproyl)oxybenzenesulonate; benizoyl caprolactam; octanoyl caprolactam;3,5,5-trimethylhexanoyl caprolactam; nonanoyl caprolactam; decanoylcaprolactam; undecenoyl caprolactam; benzoyl valerolactam; octanoylvalerolactam; nonanoyl valerolactam; decanoyl valerolactam; undecenovivalerolactam; 3,5,5-trimethylhexanoyl valerolactam; and mixturesthereof.
 7. A laundry detergent composition according to claim 1,further comprising an ingredient selected from the group consisting ofsoil release agents, suds boosters, suds suppressors antitarnish agents,anticorrosion agents and mixtures thereof.
 8. A granular laundrycomposition comprising:a) from 5% to 50% by weight of a detersivesurfactant; b) from 1% to 50% by weight of an organic or inorganicdetergency builder; c) from 0.1% to 8% by weight of apolyamide-polyamine fabric treatment agent formed from repeating unitsof the structural formula: ##STR6## wherein R₁, R₂ and R₅ are eachindependently C₁₋₄ alkylene, C₁₋₄ alkarylene or arylene or wherein R₁may not be present; R₃ is selected from the group consisting ofhydrogen, epichlorohydrin, azetidinium group, epoxypropyl group anddimethylaminohydroxypropyl group: and R₄ is selected from the groupconsisting of hydrogen, C₁₋₄ alkyl, C₁₋₄ alkaryl and aryl groups, andC₁₋₄ alkyl, C₁₋₄ alkaryl and aryl groups condensed with C₁₋₄ alkyleneoxide.
 9. A granular laundry composition according to claim 8,comprising from 1.5% to 3.2%, by weight, of the polyamide-polyamine. 10.A granular laundry composition according to claim 9, wherein the buildercomprises aluminosilicate.
 11. A granular laundry composition accordingto claim 9, wherein the surfactant comprises an ingredient selected fromthe group consisting of linear alkylbenzene sulfonates, alkyl sulfates,alkyl ethoxylates and mixtures thereof.
 12. A granular laundrycomposition according to claim 9, further comprising a peroxygen bleach.13. A laundry detergent composition according to claim 17, furthercomprising a bleach activator in a weight ratio of peroxygen bleach tobleach activator of from about 1:1 to about 10:1.